JPS6011505A - Polymerizable composite composition - Google Patents

Abstract

PURPOSE:A polymerizable composite composition which can give a composite reparing material suitable for dental use, comprising a polymerizable vinyl monomer, a specified inorganic oxide or its composite filler, an organic peroxide and an amine kept separate from the organic peroxide. CONSTITUTION:A polymerizable composition comprising the following components (a), (b), and (c), wherein (b) and (c) are kept separate from each other: (a) a polymerizable vinyl monomer, (b) an organic peroxide, (c) an amine, and (d) (i) at least one metal oxide selected form the group consisting of Groups I , II, III, and IV elements bondable with silica and a spherical inorganic oxide having silica as a principal constituent and having a particle diameter of 0.1- 1.0mum, and/or (ii) a composite filler comprising a vinyl polymer containing an inorganic oxide (i).

Description

[Detailed description of the invention]

The present invention relates to a composite composition for polymerization, and particularly to a composite composition for polymerization that, when polymerized to form a composite polymer, provides a composite restorative material suitable for dental use. More specifically, the present invention relates to a polymerization composition for use in a composite restorative material that has excellent abrasion resistance and smoothness, has a surface hardness of less than 100%, and is easy to polish. Bisphenol A glycidyl methacrylate (addition product of bisphenol A and glycidyl methacrylate, hereinafter referred to as Bia-G) is considered to have relatively small polymerization shrinkage as a dental composite restorative material, which is an example of raw fabric and composite polymer.
Abbreviated as MA. ) is mixed with a large amount of crushed glass and quartz with a particle size of several tens of micrometers in an acrylic monomer solution, and a polymerization initiator that decomposes at room temperature is added to the kudzu radish at the time of use. The m-valent compound is generally used. Composite repair materials such as those mentioned above use optically transparent inorganic powder as a filler, so compared to resin thread repair materials made by polymerizing a mixture of acrylic thread polymer and the same monomer, the polymerization time is It is characterized by excellent linear swelling coefficient and mechanical strength, without being inferior in shrinkage and transparency, and is widely used by clinicians. However, it is far inferior to natural teeth in terms of wear resistance, surface lubricity, and surface hardness, and there are many points that need further improvement. Therefore, the present inventors discovered a new inorganic oxide,
It has been found and already proposed that the above-mentioned drawbacks can be improved by using this as a dental composite restorative material. The above-mentioned inorganic oxide is composed of silica and a specific metal oxide, and is a spherical inorganic oxide having a specific particle size. The present invention uses the above inorganic oxide as an inorganic filler,
This is a composition for polymerization that is composed entirely of il+ vinyl monomers, and when it is completely polymerized to form a composite polymer, organic peroxides and amines are mixed. In addition, by using a composite polymer obtained by polymerizing the polymerization composition of the present invention, it is possible to easily polymerize the polymerization composition according to the present invention. , a composite restorative material with improved wear resistance, improved surface smoothness, and easier surface polishing.
can be obtained. That is, the present invention provides: a) Ji-polymerizable vinyl monomer b) organic peroxide C) amines and d) a) group 1, group Ⅰ, group ② of the periodic table that can be bonded to silica; An inorganic oxide (5) consisting entirely of at least one metal oxide selected from the group consisting of Group Ⅰ and silica, with a particle size of 0.1 to 1.0 μm and a spherical shape. and/or) Provide a composite composition for polymerization comprising a composite filler made of a vinyl polymer containing the inorganic oxide of a) above, and at least b) and c) above are separated so as not to mix. It is something. One component of the composite composition for polymerization of the present invention is a polymerizable vinyl monomer. The vinyl monomer &'i is not particularly limited, and known ones commonly used as dental monomers can be used. Typical examples that are generally preferably used include polymerizable monomers having an acrylic group and/or a methacrylic group. Specific examples are as follows. a) Monofunctional and vinyl monomers methyl methacrylate; ethyl methacrylate; isopropyl methacrylate; hydroxyethyl methacrylate; tetrahydrofurfuryl methacrylate; glycidyl methacrylate; and their acrylates (6) b) difunctional vinyl monomers (V aromatic compounds) Type 2.2-bis(methacryloxyphenyl)propane; 2
,2-bis(4-(3-methacryloxy)-2-hydroxypropoxyphenyl)propane; 2,2-bis(4
-methacryloxyethoxyphenyl)propane; 2,2
-Bis(4-methacryloxyjethoxyphenyl)propane; 2,2-bis(4-methacryloxytetraethoxyphenyl)propane; 2,2-bis(4-methacryloxypentaethoxyphenyl)propane; 2,2-bis (4-methacryloxydibripoxyphenyl)propane; 2(4-methacryloxyethoxyphenyl)-2(
4-methacryloxyjethoxyphenyl)propane; 2
(4-methacryloxyjethoxyphenyl') -2(
4-methacryloxytriethoxyphenyl)propane,
2(4-methacryloxydiproboxyphenyl)-2(
4-methacryloxytriethoxyphenyl)propane;
2,2-bis(4-methacryloxypropoxyphenyl)propane: 2,2-bis(4-methacryloxyisopropoxyphenyl)propane These acrylates ([1) If-f aliphatic compounds ethylene glycol dimethacrylate; diethylene glycol dimethacrylate: triethylene glycol dimethacrylate; butylene glycol dimethacrylate: neopentyl glycol dimethacrylate: propylene glycol dimethacrylate; 1,3-butanediol dimethacrylate; 1,4-butanediol dimethacrylate ;1,
6-hexanethiol dimethacrylate and their acrylates c) Bifunctional vinyl monomers trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol trimethacrylate, trimethylolmethane trimethacrylate, o and these acrylates d) Tetrafunctional vinyl monomers Seven months - Pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate, and urethane monomers having the entire structural formula shown below H (OH2)6NH 0=0 (9) C=0 H C=OC C=0 JH φ jl ? 1 0 = 0 (10) When using all types of polymerizable vinyl monomers, if the vinyl monomer has extremely high viscosity at room temperature or is solid, it may be combined with a low viscosity polymerizable vinyl monomer. It is preferable to use This combination is not limited to two types, but may be three or more types. or,
Polymers containing only monofunctional vinyl monomers do not have any bridge Ia structures, and therefore generally tend to have poor mechanical strength. For this reason, when monofunctional vinyl monomers are used, they are preferably used together with polyfunctional monomers. The most preferred combination of polymerizable monomers is a method in which an aromatic compound of a trifunctional vinyl monomer is used as a main component in combination with an aliphatic compound of a difunctional vinyl monomer. In addition, for example, a combination of a trifunctional vinyl monomer and a tetrafunctional vinyl monomer, a combination of an aromatic compound and an aliphatic compound of a difunctional vinyl monomer, a trifunctional vinyl monomer and/or a combination of a tetrafunctional vinyl monomer and a difunctional vinyl monomer, It is possible to suitably employ combinations in which all monofunctional vinyl monomers are used. Next, the composition ratio of the above vinyl monomer combinations may be determined according to need, but the composition ratios that are generally suitable for VC are as follows. (IJ difunctionality and aromatic compounds of nil monomers are 30
-80% by weight and 70-20% by weight of the same aliphatic compound (2) Trifunctional vinyl monomer is 30-100 ffi
0-70% by weight of tetrafunctional vinyl monomers (3) 30-60% by weight of aromatic compounds of difunctional vinyl monomers, 5-30% by weight of aliphatic compounds, 10% by weight of trifunctional vinyl monomers The composition ratio of the tetrafunctional vinyl monomer is preferably 0 to 50% by weight. Next, as the organic peroxide used in the present invention (1), any known organic peroxide can be used without any restriction. Typical examples include benzoyl peroxide. Parachlorobenzoyl peroxide 2,4-dichlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide; acetyl peroxide; lauroyl chloride: tertiary butyl hydroperoxide; cumene hydroperoxide; 2,5-dimethyl Examples include hexane 2,5-dihydroboroxide; methyl ethyl ketone peroxide: tajaributylbaroxybenzoate. The amines used in the present invention include primary and secondary amines.
and tertiary amines are used. For example, N, N-bis-
(2-hydroxyethyl)-4-methylaniline; N,
N-bis-(2-hydroxyethyl)-3,4-dimethylaniline; n,N-bis-12-hydroxyethyl)
-3,5-dimethylaniline: N-methyl-N -(2
-hydroxyethyl)-4-methylaniline; 4-methylaniline; N, tJ-dimethyl-P-toluidine; N
, 11-dimethylaniline; triethanolamine; P
-Amine salts of toluenesulfonic acid; amine salts of sulfinic acid, etc. (13). One component of the composite composition for polymerization of the present invention is a specific inorganic oxide. To give a specific example, Rt that can be combined with silica,
Group ■, Group ■, Group 1H, and Group ■ of the periodic table
silica and at least one metal component far from the group consisting of
It is an inorganic oxide with a diameter of m and a spherical shape.゛The particle size distribution of the inorganic oxide used in the present invention is not particularly limited, but a sharp one with a standard deviation of the distribution within 1.30 works well for the purpose of the present invention. . Both the particle size and the particle shape are very important factors, and the object of the present invention cannot be achieved if any of the conditions are absent. For example, if the particle size of the inorganic oxide is smaller than 0.1 μm, the viscosity will increase significantly when it is kneaded with the Fi-combinable navinyl monomer to form a paste-like mixture, so it is recommended to increase the blending ratio to prevent the viscosity increase. In other words, the operability becomes poor, so that it cannot be used as a material for practical use (14). Also, if the particle size is larger than 1.0 μm, is it a vinyl monomer? This is not preferable because the resin after polymerization has defects such as a decrease in abrasion resistance or surface smoothness, and also a decrease in surface [1]. Also, the standard deviation value of the particle size distribution! If the particle size is larger than 30, the twisting composition and the operability of the product may deteriorate, so it is generally preferable to use a particle size distribution with a standard deviation value of 1.30 or less. Furthermore, the inorganic oxide has a particle size of 111 and 01 to 1.
．． In the range of 0 μm, the standard deviation value of the particle size distribution is 1.3
Even if the particle size is within 0, unless the particle shape is spherical, the effects of the present invention as described above will be satisfactory, especially in terms of wear resistance, surface smoothness, surface hardness, etc. It can't be. The method for producing the inorganic compound is not particularly limited and any method may be employed, but the following method is generally preferably employed. A hydrolyzable organic compound of at least one metal selected from the group consisting of a hydrolyzable organosilicon compound and a hydrolyzable metal of Group 1, Group 1], Group 1n, and Group II of the Periodic Table. and all the tr mixed solutions are alkaline, which dissolves the silicon compounds and organic compounds of metals of Groups 1, II, and IV of the periodic table, but substantially does not dissolve the reaction products. Selected from the group consisting of metal oxides of Group 1, Group Ⅰ, Group Ⅰ and Group Ⅰ of the Circular Table, which are obtained by adding to mollusc, hydrolyzing it and precipitating the reaction product. A method for producing an inorganic oxide whose main constituents are at least one metal oxide and silica is preferably employed. In general, it is preferable to completely reduce the silanol groups on the surface of industrially obtained inorganic oxides in order to maintain surface stability. For this purpose, after drying the spherical inorganic oxide,
A method of firing at a temperature of 0,000° C. is often preferred. During the calcination, some of the oxides may sinter and agglomerate, so it is usually preferable to use an exponent, vibrating hall mill, or pulverizer to soothe the agglomerated particles. Also generally before iic! In order to maintain stability, the calcined inorganic oxide is most preferably used after surface treatment using an organic silicon compound. The surface treatment method described above is not particularly limited and may be performed by any known method, such as using an inorganic oxide and a known organosilicon compound such as γ-methacryloxypropyltrimethoxysilane or vinyltriethoxysilane in a mixed solvent of alcohol/water. A method is adopted in which the solvent is completely removed after contact for a period of time. The particle size and shape of the inorganic oxide used in the present invention can be confirmed by taking a W4 microscopic photograph, and the standard deviation of the particle size distribution can be determined by the unit direction of the microscopic photograph. It can be calculated from the number of particles existing within the unit field of view of the microscope and their respective diameters using the calculation formula described below. The above-mentioned microscopic photograph may be any photograph as long as the particle shape of the inorganic oxide can be observed, but in general, scanning electron micrographs, transmission electron micrographs, etc. are suitable. In addition, when the inorganic oxide is mixed with another liquid substance such as a polymerizable monomer to form a paste mixture, the liquid substance is completely extracted (17
) After increasing the size of the inorganic oxide, it is best to use the same spherical operation as described above to check the properties of the inorganic oxide on all axes. As mentioned above, the inorganic oxide used in the present invention is a spherical particle, but whether or not it is spherical can be confirmed by measuring the ω1 product of the inorganic oxide in addition to the above-mentioned microscope. I can do it. For example, particle size 0.1-10 μm
The inorganic oxide in the range 1 has a specific surface area of 4.0 to 4.
If it is about 0.0 m/g, the specific surface area calculated by subtraction assuming a perfect # type matches. Therefore, the inorganic boride used in the present invention has a specific surface area of 4.0 to 40.0 m'/9.
It is preferable to use the entire range of . As a component of the composite composition for polymerization of the present invention, a platform filler made of a vinyl polymer containing an inorganic oxide can be used instead of the nt+ inorganic oxide. A filler mixture in which a composite filler is added to the inorganic oxide can also be used. The method for producing the composite filler is not particularly limited, and any method may be used. In general, the inorganic plate, that is, the inorganic oxide having a particle size of 0.1 to 1.0 μm and a spherical shape (18), is completely mixed with a polymerizable monomer, and a paste is MALed and polymerized. A viscous filler consisting of a vinyl polymer containing all of the above inorganic oxides is obtained. Methods for making the entire paste include kneading it by hand, crushing it with your fingers, and using a mechanical sound such as a rubber roll or kneader. The mixing ratio is preferably 50 to 90% by weight of the inorganic compound and 10 to 50% by weight of the vinyl monomer. When mixing, a volatile solvent that does not affect the polymerizable vinyl monomer and the inorganic oxide may be added to improve the compatibility. The solvent used is methanol, ethanol, and improper tool. Examples include benzene and ether. Next, in the step of polymerizing the paste, the paste may be directly polymerized, but if the paste contains all the air bubbles before polymerization, or if a solvent is used during the preparation of the paste. For this purpose, it is better to either vacuole or remove all the solvent. Therefore, it is preferable to place the vcl-L1 paste under reduced pressure. Next, there is a method of adding a polymerization initiator when fixing the paste. Further, the polymerization humidity is generally preferably in the range of room temperature to 200°C. ■

[If the method involves heating without adding the entire polymerization initiator, the polymerization time will be longer. Depending on the type of polymerization initiator, the composite filler may easily discolor, so it is better to choose one that is resistant to discoloration. The addition history of polymerization initiators is as follows:
The vinyl monomer A preferably has a content in the range of 0.01 to 2%. Typical polymerization initiators are those that generate radicals to polymerize polymerizable monomers, and in addition to the above-mentioned organic peroxides, azo compounds such as azobisisobutyronitrile and tributylboric acid are used as typical polymerization initiators. Organometallic compounds are also used. Furthermore, a photosensitizer can be used as a polymerization initiator. Examples of the photosensitizer include benzoin and benzoin methyl ether. Examples include benzoin ethyl ether, acetoin benzophenone, P-chlorobenzophenone, and P-methoxybenzophenone. In order to prevent the polymer from discoloring, it is preferable to carry out the polymerization in an inert gas atmosphere of nitrogen or argon, and to apply pressure to reduce the total percentage of air bubbles mixed in the paste. The degree of pressurization is not particularly limited, but may generally be 1 to 5 degrees. Next, the composite filler preferably has a predetermined average particle size and particle size range. If the particle size is large, the paste obtained by completely mixing the composite filling powder and vinyl monomer will be rough;
On the other hand, if the particle size is small, the paste becomes viscous. usually,
The particle size is in the range of 0.1 μm to 150 μm, preferably the average particle size is in the range of 1 μm to 40 μfi+7+. The composite filler having the above average particle size and particle size range is
It is obtained by bulk polymerizing a paste made by mixing an inorganic oxide and a polymerizable vinyl monomer, and then pulverizing the polymer. The grinding method is not particularly limited, but ball mill,
Mmm. A crusher such as an m-motion ball mill or a jet crusher is preferably used. By using a composite filler, in addition to the excellent effects as a combination composition obtained when all inorganic compounds are used as described in (21) above, a whole new effect can be exhibited. For example, a paste obtained by mixing a composite filler and a polymerizable vinyl monomer has a lower viscosity than a paste obtained by mixing the inorganic oxide and a vinyl monomer, making it easier to knead. can be opened. One of the evaluations of this viscosity is expressed by the length of stringiness of the paste. In general, the paste obtained by mixing the inorganic compound and the polymerizable vinyl monomer has a long stringy length, and the paste obtained by mixing the composite filler and the polymerizable vinyl monomer has a long stringy length. Sa is short. When the filler mixture is used as one component of a composite □ composition in addition to the inorganic oxide, the length of rods and strings containing a large proportion of the composite filler tends to be short. When kneading, the viscosity of the paste is varied within an appropriate range. The stringing length at that range of viscosity is 0-20 steel. The proportions in the filler mixture to achieve a suitable range of viscosity are 0 to 80% by weight of the inorganic (22) oxide and 20 to 100% by weight of the filler.
Preference is given to percentages by weight. The ingredients of the present invention are as explained above,
In addition, components such as ultraviolet absorbers such as 2-hydroxy-4-methylbenzophenone and pigments can be optionally added. Next, a method of mixing the composite composition for polymerization when the composite composition for polymerization of the present invention is completely polymerized to obtain composite polymer 2 will be explained. First, the mixing ratio of each component of the present invention is preferably in the following range. The mixing ratio of a) (Di polymerizable vinyl monomer and d) inorganic oxide and/or filler is 10 to 7.
It is appropriate that d) is in the range of 30 to 90% by weight, and more preferably &) is in the range of 20 to 40% by weight, iiN%
and d) is 60 to 80% by weight Mk%. The amount of the organic peroxide (b) is appropriately released depending on the polymerization time, but it may normally be in the range of 0.1 to 3% based on the polymerizable vinyl monomer (a). The length of the amine in C) above is selected appropriately depending on the rate of λ combination, but usually a
) may be in the range of 0.1 to 5 times or more with respect to the polymerizable vinyl monomer. ! When storing the polymerizable vinyl monomer (L) mixed with b) or C), it is preferable to use all the polymerization inhibitors in order to maintain the storage stability of the polymerizable vinyl monomer. The polymerization inhibitor used is not particularly limited, but typical examples include known phenol compounds such as 2,5-di-tert-butyl-4-methylphenol and hydroquinone 7-methyl ether. Next, although the mixing of the composite composition for polymerization is not particularly limited, typical embodiments will be shown. The composition for use in table 1 of the present invention must be VC-separated to avoid mixing at least the organic peroxide (b) and the amines (C) during storage. When b) and C) are mixed, radicals are generated, and if the polymerizable vinyl monomer of a) is present therein, a polymerization reaction occurs. Therefore, b) and 0) must be mixed when polymerizable and nil monomers 1i of a) are polymerized. The above method of differentiation is not limited in any way as long as it is a method that does not mix at least b) and C). For example, the most common method is to place them in separate containers and seal them. The composition for polymerization of the present invention has different embodiments as in the conventional method, and each is mixed at the time of polymerization. (υ a)# b) and Q)l (1) are each individually distinguished, and they are all mixed together during polymerization. (2) &)+b)+a) Mix everything and make the paste,
This paste and C) are separated and C) is mixed with this paste during polymerization. (3) a) + o) r a) T-Mix to make a complete paste, this paste and b) are distinguished, and b) is mixed with this paste when polymerizing. (4) a), b), a) T-Mix to make paste A, and on the other hand, make a mixture of a) and C), and this (25) Paste and mixture are distinguished, and when polymerized, they become paste. Mix the above mixture. (5) Make a mixture of a) and b), -ha). c), (1) f are mixed to make a paste, this mixture and the paste are separated, and the above mixture is completely mixed into the paste during polymerization. (6) a) + b), a) are all mixed to make paste A, while a), c), and d) are mixed to make paste B, both pastes are distinguished from each other, and when polymerized they form a circle. Mix both pastes. Among the above mixing modes, mode (6) is the most preferred;
In this case, the value of the Idol paste differs depending on the polymerization time, but it is generally preferred to be equal to 1 for operational reasons. In order to explain the real milk spoon shape more specifically, the above aspect (6) will be specifically described, but other rolling balls may also be implemented according to the following description. Paste Eight is a mix of the queen's ingredients in their respective proportions. (26) Paste A; a') m combination Iil &'t i vinyl monomer 10
-F0 weight ratio b) Organic peroxide 0.001 to 2% by weight d) a) From Group 1, Group II, Group II, and Group III of the periodic table that can be bonded to silica The main constituents are at least one metal oxide selected from the group consisting of silica and a particle size of 0 to 1. A composite filler consisting of an inorganic oxide whose shape is spherical in Opm and/or a vinyl polymer containing the inorganic oxide of above A) 30 to 90 M% On the other hand, the base) B has the following components: They are mixed in equal proportions. Paste B; ! L') Same as a) of Paste A 10-70% by weight C) Amines o, ooi to 3,5% by weight d' 30-90% by weight Same as d) of Paste A Above base) A and base ) B are separated by, for example, sealed in separate containers so that they do not mix during storage. Then, by mixing paste A and paste B, a polymerization reaction of the vinyl monomers is started, and a wedge polymerization product is formed. This embodiment consists of a) a liquid component and b) a solid component.
re) and a) are mixed in advance to form paste A and paste B. Therefore, there is an advantage that polymerization can be carried out by a simple operation of mixing the pastes together. The composite composition of the present invention is not inferior to conventional compositions in mechanical strength such as compressive strength, has excellent abrasion resistance or lubricity as shown in Table 1 (L), and has high surface hardness and It has many excellent features such as being very easy to polish. However, the reason for these features is currently not clear, but the inventors have found the following contradiction. That is, firstly, the shape of the particles is spherical and the particle diameter is 0.
．． By using all combinations of inorganic oxides with a uniform particle size of 1 to 1.0 μm and preferably with a standard deviation value of particle size distribution within 1.30, it is possible to improve the conventional method of simply having a wide particle size distribution and shape. Compared to the case of using uneven filler material, the non-oxide is more uniformly and densely packed into the composite resin obtained by curing, and secondly, the particle size range is from 0.1 to By using a filler with a particle size within the range of 1.0 μm, the polished surface of the composite composition of the present invention becomes smoother than when using a conventional inorganic filler with a particle size of several tens of μm. The total specific surface area of the filler is smaller than when using an ultrafine particle filler whose main component is fine particles of several tens of nanometers, so it is possible to fill a large amount of filler under conditions with appropriate operability. There are possible reasons for this. By completely blending the specific inorganic oxide and the polymerizable vinyl monomer, the composite composition of the present invention exhibits a number of previously unanticipated advantages as described above. (29) Furthermore, by employing all of the above-mentioned mixing modes, operations are simplified in preparing a composite composition. For example, in the case of mixing embodiment (6), especially when the composite composition for polymerization of the present invention is used as a dental restoration material, the doctor takes out the required amount of both pastes and mixes both pastes completely. , the tooth can be immediately filled in the area to be repaired. After filling, polymerization can be carried out in a few minutes without the need for heating, making it convenient. As described above, when the composite composition for polymerization of the present invention is used as a dental composite restorative material, many excellent effects can be obtained. The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples. In addition, measurements of various properties of inorganic oxides (particle size 2 particle size distribution 11 specific surface area) and physical properties of composite polymers (compressive strength 1 bending strength, toothbrush abrasion depth The following method (30) was used to measure the viscosity of the paste (1) surface roughness (1) surface hardness) and to evaluate the viscosity of the paste. (1) Standard deviation value of particle size and particle size distribution, scanning electron micrograph of powder, its '1f - number of particles observed within the true unit field of view (nJ, and particle size (diameter
) is calculated using the following formula. Standard deviation value=□ (2) Specific surface area Shida Kajiki Kogyo ■Jinren surface measuring device 5A-1000 was used. The measurement principle is the BKT method. (3) Compressive Strength A composite polymer test piece was prepared by immersing it in water at 37° C. for 24 hours. Its size and shape are cylindrical with a diameter of 6 mm and a quality of 12 pieces. This sample #1 was attached to a testing machine (σTM-5T manufactured by Toyo Hardwin), and the compressive strength was measured at a crosshead speed of 10 cm/sequence. (4) Bending strength: 37°C, immersed in water for 24 hours. was used as a test piece of the composite polymer. Its size and shape were 2 x 2 x 25 m+ prismatic.For the bending test, 1 was equipped with a bending test device Zentoyo Baudwin Mfg. TM-5T [equipped with (5) Depth of toothbrush wear and surface roughness: A test piece of composite polymer was prepared by immersing it in water for 24 hours at 37°C. Its size and shape is a plate of 1.5 x 10 x 10 mm.
After 500 m of wear, the surface roughness meter (Surfcom A-j0
0), the ten-point average roughness was calculated. Further, the wear depth #'i was calculated by dividing the wear weight by the density of the composite polymer. In addition, in this test method, the toothbrush wear depth of standard methyl methacrylate resin was 1d60 μm. (6) Surface hardness: 37°C, immersed in water for 24 hours A test piece of all composite polymers. Its size and shape are 25 x 10 m disc-like. The measurement was conducted using a micropurinel hardness test. Insert a glass rod with a diameter of 5 wx and a length of 100 ta into the smooth surface of the whole paste at an angle of 45 degrees to a depth of 5 ta. Fix the container and move the glass bowl all vertically at a constant speed (
10 cm/aθC) to cause stringiness of the pulling paste. The length until the threads break is the maximum length (33) of all threads, and this is used to evaluate the lA't properties of the paste. Tensilon (manufactured by Toyo Baudouin [7TM-5T)] was used to raise the crow's head. The abbreviations used in the examples are as follows unless otherwise specified. Ble-aMh; 2a 2-his(4-(2-hydroxy-3-methacryloxyphenyl)propane B15MPP; di(4-methacryloxyethoxyphenyl)propane rEGDMA; ) diethylene glycol dimethacrylate DEGDMA; diethylene glycol dimethacrylate TMPT z trimethylol Propandolyacrylate TMM-3M; Hentaerythritol trimethacrylate 1, rMM -4M p Pentaerythritol tetrame(34) Tafrylate M MA + Methyl methacrylate NPG z Neopentyl glycol dimethacrylate 1-
tH (OH2)6tJH 0=0 0=0 C=0 Example 1 Production method of inorganic oxide 0.1% hydrochloric acid 4.09 and tetraethyl silicate 158
g (81 (002H5) 4. Product name manufactured by Nippon Colfut Chemical Co., Ltd.; Ethylsilifut 28) and methanol 1.2
1, and this solution was hydrolyzed at room temperature for about 2 hours with stirring. Then, this total tetrabutyl titanate (
Ti (0-n04H9)4, manufactured by Nippon Soda) 40.9.
A mixed solution of tetraethyl silicate hydrolyzate and tetrabutyl titanate was prepared by adding vL of a solution of Impropatol O and FM to 9' with stirring. Next, 2.5 methanol was introduced into a glass reaction vessel with an internal volume of 101 mm equipped with a stirrer, and 500 g of ammonia aqueous solution (#a 25 wt%) was added thereto to prepare an ammoniacal alcohol solution. As a silicon compound solution for making whole seeds, a solution of 4.09% tetraethyl silicate dissolved in 100ml of methanol was added over a period of about 5 minutes, and 5 minutes after the addition was completed, the reaction solution turned slightly milky white ( 36) Then, the above mixed solution was added to the reaction vessel over a period of about 2 hours while maintaining the total lag of 20°C to completely precipitate the reaction product. Thereafter, a solution containing 1 zsy't of tetraethyl silicate dissolved in 0.57 K of methanol was added over a period of about 2 hours to the system in which the reaction product had precipitated. After the addition was completed, stirring was continued for another hour, and then the milky white reaction solution was removed using an evaporator, and coarsely
A whole milky white powder was obtained by drying at 900°C under reduced pressure.Furthermore, this milky white powder was fired at 900°C for 4 hours, and then dispersed in an agate mortar to obtain an inorganic dispersion of silica and titania as constituent components. I got everything. From observation using a scanning electron microscope, this inorganic oxide has a particle size in the range of 0.10 to 0.2011 m (F), an average particle size of 0.13 μm, a true spherical shape, and a standard deviation value of the particle size distribution. is 1.08, and the specific surface area is 20ze/I
Met. The obtained inorganic oxide was roughly surface-treated with γ-methacryloxypropyltrimethoxysilane. (37) For surface treatment, 8 weight percent of γ-methacryloxypropyltrimethoxysilane Th was added to the non-thm compound, and after refluxing at 80°C for 2 hours in a water-ethanol solution, all the solvent was removed using an evaporator. , and further by a method of vacuum drying. Next, 10 g of this surface-treated inorganic oxide, Bis-G
A monomer mixture of MA and T]IceDMA (
Mixing ratio Big-GHA 60 weight attack, TFiGDM
A40 weight it%) 3.6p, benzoyl peroxide as organic peroxide (z in the above and nil monomer mixture
%) and 2,5-di-tert-butyl-4
- methylphenol (0.1 in the vinyl monomer mixture)
% by weight) were mixed to obtain a paste. (This entire paste will be referred to as Paste B) 1all of the same inorganic oxide as above, 3.6L of the above vinyl monomer mixture, N,N-bis-(2-human tetraxyethyl)-4-methylaniline as the amine (the above and vinyl monomer mixture) 1.2% by weight in the mixture) and 2,5-di-tert-buty(38)-4-methylphenol (0.02% by weight in the above vinyl monomer mixture) to obtain a paste. (This paste is called Paste A) Paste date and base)
An equal amount of Aksotl was taken, mixed, and stirred for 30 seconds at room temperature. As a result of measuring all the physical properties of the composite material, the compressive strength was 3.800.
%, bending strength 810-1, surface roughness 0.4 μam, surface hardness 62.0. The toothbrush wear depth was 4.0 μm. The viscosity of base) B was 80 cIn. Examples 2 to 6 All methods were the same as in Example 1 except that the composition of the vinyl monomer mixture shown in Table 1 was used, and N,N-dimethyl-P-toluidine was used as the amine (base) A and base)
B Complete preparation. Both pastes were weighed in equal numbers, mixed and kneaded for 30 seconds at room temperature, and the physical properties of the polymerized polymer and the viscosity of base) B were all measured. The results are shown in Table 1. (39) Examples 7 to 11 Preparation method of inorganic oxide Tetraethyl silicate (Si (oo2)f5)4 distilled with 05% Jffl 1.8F, Japan: l Le:
I-) Manufactured by Kagaku Co., Ltd. Product name: Ethyl silicate 28) 104
,! i' Total methanol was dissolved in 0.2 methanol and the solution was hydrolyzed at room temperature with stirring for about 1 hour. Then, this was added with tetrabutyl titanate (Ti (0-no4H0
) 4 Nippon Soda) 17.0.9 isopropanol 1.
A mixed solution of tetraethyl silinate hydrolyzate and tetrabutyl titanate was added to the solution dissolved in 0.01 with stirring.Next, 7.8 g of barium bisisobenoxide and 104 y of tetraethyl silicate were added.
and 0.2 g of aluminum triSθe-butoxide in methanol 1. OIc was dissolved and the solution was allowed to flow for 30 minutes at 90°C under a nitrogen atmosphere. Thereafter, the temperature was returned to the temperature, and this was used as a mixed solution (B). Kirani mixed solution (A
) and the mixed solution (B) were mixed at room temperature to obtain a mixed solution (Q). (41) Next, a glass reaction vessel with an internal volume of 101 mm and equipped with a stirrer was completely filled with 254 methanol, and 500 g of ammonia aqueous solution (concentration 25 wt%) was added to ib the ammoniacal alcohol solution. The mixed solution (0) prepared previously was added over about 4 hours while maintaining the temperature of all reaction vessels at 20°C. A few minutes after the addition started, the reaction solution became milky white. After the addition was completed, stirring was continued for 1 hour, the solvent was removed from the milky white reaction solution using an evaporator, and the mixture was further dried under reduced pressure at 80°C to obtain a milky white powder. Further, this milky white powder was calcined at 900 DEG C. for 4 hours, and then agglomerated in an extractor to obtain an inorganic saponified product containing silica, titania, and barium oxide as the main constituents. As a result of observation using a scanning electron microscope @ four mirrors, the shape of the inorganic oxide was h-shaped, and its particle size was 0.12 to 026 μm.
The particle diameter was within the range of 1.06. Further, the specific surface area determined by the BET method was 30 ml/g. According to X-ray analysis, a gentle mountain-shaped (42) absorption was observed at approximately 2° = 25°, indicating that the entire surface of the amorphous structure is located at (42).
I have been ordered to do so again. This inorganic oxide was further surface-treated with γ-methacryloxypropyltrimethoxysilane in the same manner as in Example M]. Next, the same method as in Example 1 was carried out except that this surface-treated inorganic oxide, the vinyl monomer mixture shown in Table 2, and lauroyl peroxide (2,5 weight fj +%) were used as the organic peroxide. Then, PACE) A and PACE) BTh were prepared. Both pastes were weighed equally and kneaded for 1 minute at room temperature, and the viscosity of the polymerized composite polymer and paste B was measured. The results are combined and shown in Table 2. (43) Examples 12 to (6 Production method of @oxide-free 52 g of tetraethyl silicate similar to that used in Example 1 and zirconium tetrabutoxide (Zr
(004H9)4) ts, 6E was dissolved in 0.21% of isopropyl alcohol, and the solution was heated at 100°C.
It was refluxed for 30 minutes under nitrogen atmosphere. The cherry blossoms were returned to room temperature and used as a total mixed solution (A). Next, 52 g of tetraethyl silicate and 6.1 F't of strontium bismethoxide and 0.2 j of methanol
? This solution was refluxed for 30 minutes at 80° C. under a nitrogen atmosphere. After that, the temperature was returned to room temperature, and the mixed solution (B
). The mixed solution (A) and the mixed solution (B) were mixed at room temperature to form a gold mixed solution (01).Next, a glass reaction container with a content of 111 to A' equipped with a stirrer was filled with 2.41 methanol. Add 500 g of ammonia water (concentration 25% by weight) to this to prepare an ammoniacal alcohol solution, add the previously prepared mixed solution (Q) t- to this solution, and while keeping the reaction vessel at (45) 20°C, It was added over about 4 hours to precipitate the reaction product.Thereafter, a solution consisting of 501/methanol and 0.5/methanol was added to the system in which the reaction product had precipitated over about 2 hours. History after the completion of addition! After stirring for 1 hour, the solvent was removed from the milky white reaction solution using an evaporator, and the milky white powder was further dried under reduced pressure. From microscopic observation, the particle size is in the range of 0.10 to 0.025 μm, and the average particle size is 0.
．． 17 μm, the shape is spherical, the standard deviation value of the particle size distribution is 1.25, and the specific surface area is 26 rrt/11
Met. Further, this milky white powder was calcined at 900° C. for 3 hours and crushed using a rig crusher to obtain an inorganic oxide whose main components were silica, zirconia, and strontium oxide. This inorganic oxide was further surface-treated with γ-methacryloxypropyltrimethoxysilane in the same manner as in Example 1. Next, this surface-treated inorganic oxide was mixed with benzoyl peroxide (1,5% by weight) to the vinyl monomer mixture shown in Table 3 (46) and to the organic peroxide. Fourteen pastes A and B were prepared in the same manner as in Example 1 except that all ethers were used. Both pastes each have sweetfish, 3
Physical properties of the tack mixture and viscosity of paste B, which were kneaded at room temperature for 0 seconds and polymerized. was measured. The results are shown in Table 3. (47) Examples 17-21 Method for producing inorganic (2) compounds. 4.09 g of 0.1% hydrochloric acid and 158 g of the same tetraethyl silicate used in Example 1 were dissolved in 1.27 g of methanol, and this solution was hydrolyzed at room temperature with stirring for about 1 hour. Thereafter, this was mixed with 40% tetrabutyl titanate.
9't isopropanol o, 5zVc dissolved in 'fe solution was added with stirring to form a mixed solution of tetraethyl silicate hydrolyzate and tetrabutyl titanate (AJ'
was prepared. On the other hand, sodium methylate 0.2.9'
i Methanol 0.5/K Dissolved solution Total mixed solution (
A) was mixed to obtain a total mixed solution (B). Next, introduce Improper Tool 15A' into a glass reaction vessel of 1 (l) with a stirrer and add 50 (l) of ammonia aqueous solution (concentration 25%) to prepare an ammonia alcohol solution. A solution of tetraethyl silicate 5809 dissolved in methanol 1001 was added to this over about 10 minutes, and immediately after the addition was complete (49
) The reaction product was precipitated by adding the mixture solution (BJ') prepared previously by VC over a period of about 6 hours while keeping the temperature of the reaction vessel at 20°C.Then, 128 g of tetraethyl silicate and Sodium methylate o, 1g
A solution prepared by dissolving the above reaction product in methanol 051 was added over about 3 hours to the thread on which the reaction product had been precipitated. After addition, heat 1
After continuous stirring, the liquid medium was completely removed from the milky white reaction solution using an evaporator, and the mixture was further dried at 100°C under reduced pressure to obtain a milky white powder. Further, this milky white powder was calcined for 1 hour at 1000 DEG C., and then loosened with a sieve machine to obtain all of the inorganic compounds containing silica, titania, and sodium dispersion. The particle size of this inorganic oxide was found to be in the range of 0.20 to 0.40 μm, with an average particle size of 0.
．． The particle size was 28 μm, the shape was spherical, the standard deviation value of the particle size distribution was H1.25, and the specific surface area was 5 g/g. The obtained inorganic oxide was further surface treated using γ-methacryloxysilane in the same manner as in Example 1 (50). Next, this surface-treated inorganic oxide, the vinyl monomer mixture shown in the fourth example, and amines were added to N,N-dimethyl-
Paste A (7 base) B was prepared in the same manner as in Example 1 except that P-toluidine (15% by weight) was used. Physical properties and pace of the composite polymer obtained by taking both pastes in equal amounts, kneading them in a room flow for 30 seconds, and polymerizing them)B)
The viscosity was measured. The results are shown in Table 4. (51) Example 22 Manufacturing method of filler material BiS-
Binary between GMA and TEGDMA /I= -T-/
Y-(F) mixture (mixing ratio is Bis-GMA 60
weight it%, TlcGDMA 40 mM%), asobisisobutyronitrile (o, sm> per 100 parts by weight of the vinyl monomer mixture) and ethanol (15 parts by weight per 100 parts by weight of the vinyl monomer mixture) to make a sufficient amount. By kneading, all phases of the paste were obtained. This paste was placed under a total vacuum to remove all air bubbles and ethanol. The filling of inorganic oxide in the paste after all air bubbles and ethanol was removed was 78.01!Xit%. Thereafter, this paste' was subjected to a polymerization humidity of 120% under nitrogen pressure of 5Y!
C. for 1 hour to obtain a polymer. After crushing this polymer in a mortar to a size of 5u or less in diameter,
It was ground in a machine for 1 hour. After pulverization, a composite filler that passed through a 250-mesh sieve was obtained. The composite filler had a specific gravity of 2.21 and a surface hardness of 72 (53). Next, a filler mixture of the above composite filler and the inorganic oxide used in Example 1 (the mixing ratio was 5 ojkii of the composite filler) was prepared.
&%, inorganic oxide 50%) 110IlIB1 day-G
Vinyl monomer mixture of MA and I'EGDMA (mixing ratio: Bia-GMA 60% i&%, Tll:G1
)MA40wt%) 3.2L benzoyl peroxide (2.0i (it%) in the vinyl monomer mixture) and 2,5-ditert-butyl-4-methylphenol (01wt% in the vinyl monomer mixture) were mixed. (This paste is referred to as paste B) Filler mixture similar to the above 1011 Vinyl monomer mixture 3.2Ji'q ","-bis-(2-hydroxyethyl)-4-methylaniline ( (1.2% by weight in the vinyl monomer mixture) and 2.5-di-tert-butyl-4-methylphenol (0.02ml d% in the vinyl monomer mixture) were mixed to form a paste. This paste is referred to as Paste A.) (54) Paste B and Paste) AI - The physical properties of the composite polymers, which were kneaded and polymerized in equal basins for 30 seconds at room temperature, were measured. As a result, the compressive strength was 3710! XI, bending strength 890~
, surface roughness was 0.5 μm, surface hardness was 62, and toothbrush adhesive depth was 55 μm. The viscosity of paste B was 5 cIn. Examples 23-27 All pastes were made in the same manner as Example 22, except that the filler mixture and vinyl monomer mixture shown in Table 5 were used.
A and pace) B were prepared. Both pastes were taken in equal proportions, kneaded and polymerized at room temperature for 30 seconds, and the physical properties of the composite material and the viscosity of Paste B were measured. The results are shown in Table 5 for all units. (55) Examples 28 to 62 - Manufacturing method of composite filler Example 70 The vinyl monomer mixture of Example 20 and Lauroy At peroxide (
A paste was obtained by blending all of the components (0.2 parts by weight per 100 parts by weight of the vinyl monomer mixture) and ethanol (10 parts by weight per 100 parts by weight of the vinyl monomer mixture) and thoroughly kneading them. This paste was placed under air to remove air bubbles and ethanol. The filling amount of inorganic oxide in the paste after all air bubbles and ethanol have been removed is 76% by weight.
Met. Thereafter, this paste was polymerized at 90° C. for 1 hour under argon pressure for 3 hours to obtain a polymer. This polymer was ground in a ball mill for 5 hours, and then further ground in a TM soaking machine for 1 hour. The composite filler passed through a 400 mesh sieve after pulverization had a specific gravity I/' of 1140 and a surface hardness of 65. Next, paste) A and paste B'ft (57) were prepared in the same manner as in Example 22, except that the filler mixture and vinyl monomer mixture shown in Table 6 were used. Equal parts of both pastes were kneaded and polymerized at room temperature for 30 seconds, and the physical properties of the composite polymer and the viscosity of paste (H) were measured. The results are shown in Table 6. (58) Examples 63 to 67 Process for producing composite filler Example 120 To the surface-treated IJII-free oxide, the tonyl monomer mixture of Example 3 and methyl ethyl lactone peroxide (1 part per 100 parts by weight of the vinyl monomer mixture) were added. A paste Tt was obtained by blending 20 parts by weight of methanol (20 parts by weight based on the vinyl monomer mixture tooJfIJim) and thoroughly kneading the paste.The paste was placed under a total vacuum to remove air bubbles and methanol. After removing air bubbles and methanol, the filling amount of inorganic oxide in the paste was 80% by weight.Then, this paste Yt2V was polymerized at 120°C for 4 hours under nitrogen pressure to obtain the main polymer. After pulverizing for 6 hours in a combined whole ball mill, it was further pulverized for 1 hour in a crusher. After pulverization, a composite filler that passed through a 200-mesh sieve was obtained. The specific gravity of the composite filler was 25.
1, and the surface hardness was 75. Paste A and paste Byt were prepared in the same manner as in Example jC60) 2 and f#i except that the filler mixture and vinyl monomer mixture shown in Table 7 were used. Both bases) 1 - Take equal amounts of each and knead in a room for 30 seconds. [Combined composite polymer and base]
The viscosity of B was measured. The results are shown in Table 7 for all units. (61) Examples 68-42 Manufacturing method of composite optical TF4 phase Example 170 Inorganic oxide subjected to surface treatment, 6 practical examples x 9
of vinyl monomer mixture and benzoyl peroxide (011 parts per 100 parts of vinyl monomer mixture)
A paste was obtained by blending and thoroughly kneading tC. This paste was placed under vacuum to remove all air bubbles. The amount of inorganic oxide in the paste after all air bubbles were removed was 655 parts by weight. Afterwards, this paste was heated under 5 liters of nitrogen pressure.
Polymerization was carried out at 90° C. for 4 hours to obtain a polymer. This polymer was pulverized for 1 hour in a full vibrating ball mill, and then further pulverized for 1 hour in a crusher. A composite filler of 6H powder and 250 mesh was obtained. The composite filler had a Higuan Fi of 2.01 and a surface hardness of 70. Next, paste A and paste B whole sea bream were prepared in the same manner as in Example 17 except that the filler mixture and vinyl monomer mixture shown in Table 8 were used. both bases) Th
The viscosity of each of the composite polymers and Hihes) B which were kneaded and polymerized at room temperature for 1 minute was measured. The results are shown in Table 8. (65) Example 43 An inorganic oxide was obtained in the same manner as in Example 1 except for the raw material composition and firing conditions of the mixed solution shown in Table 1. Its physical properties are shown in Table 1. Next, a composite polymer was obtained in the same manner as in Example 1 except that the inorganic oxide and vinyl monomer mixture shown in Table 1 was used. The physical properties of the obtained composite polymer were measured and shown in Table 1. Example 44 An inorganic oxide was obtained in the same manner as in Example 1 except for the raw material composition and firing conditions of the mixed solution shown in Table 10. Its physical properties are shown in Table 10. Next, a composite polymer was obtained in the same manner as in Example 1 except that the inorganic oxide and vinyl monomer mixture shown in Table IO was used. The physical properties of the obtained composite polymer were measured and shown in Table 10. Example 45 An inorganic oxide was obtained in the same manner as in Example 7 except for the raw material composition and firing conditions of the mixed solution shown in Table 1 (1).The physical properties are shown in Table 11. An encapsulant polymer was obtained in the same manner as in Example 7 except that the inorganic oxide and vinyl monomer mixture shown in (1) was used.The physical properties of the obtained composite polymer were measured and shown in Table 11. Example 46 A composite: jf, ring material was obtained by the manufacturing method of Example 22 except that the inorganic oxide of the example shown in the composite filler column of Table 12 was used. A composite polymer was obtained in the same manner as in Example 22 except that the inorganic oxide and vinyl monomer mixture shown in Example 12 was used.The physical properties of the obtained composite polymer were measured and shown in Table 12. Example 47 A composite filler was obtained by the manufacturing method of Example 28 except that the inorganic oxide of the example shown in the column of composite filler in Table 13 was used. A composite polymer was obtained in the same manner as in Example 28 except that #i organic oxide and vinyl monomer mixture were used.The physical properties of the obtained composite polymer were measured and shown in Table 13. 48 A composite filler was obtained by the manufacturing method of Example 33 except that the inorganic oxide of the example shown in the column of composite filler in Table H was used.This composite filler and the inorganic oxide and A composite polymer was obtained in the same manner as in Example 33 except that a vinyl hexamer mixture was used.The physical properties of the obtained composite polymer were measured and shown in the table. ) -48-

Claims (1)

[Claims] (1) A composite composition for polymerization consisting of the following ') + b) + a) and d), in which at least b) and C) are separated so that they do not mix. a) Polymerizable vinyl mono V- b) Organic peroxide G) Amines d) (a) From Group 1, Group Ⅰ, Group Ⅰ and Group of the Periodic Table that can be bonded to silica an inorganic oxide whose main constituents are at least one metal oxide selected from the group consisting of silica, a particle size of 0.1 to 1.0 μm, and a spherical shape; A composite filler made of a vinyl polymer containing all of the inorganic atomized substances mentioned in (a) above. (2) A patent claim in which group A, which is a mixture of a) * b) and a), and group B, which is a mixture of a) r c) + a'), are separated so that they do not mix. A composite composition for polymerization according to range (1). Group A: a) Fi combination possible [vinyl monomer 10 to 70% by weight b) Organic peroxide o, oot to double it% d) (a) Group II of the periodic table, group II of the periodic table that can be combined with silica
The main constituents are at least one metal oxide selected from the group consisting of Group 1, Group 1 and Group Composite filler consisting of a spherical inorganic oxide and/or (b) a vinyl polymer containing all of the inorganic compounds of (a) above Group B 30-90% weight; al) Same as a) above 10-70 nails Amount % C) Amines 0.001-3.5% by weight a+) Same as d) above
30-90% by weight